Sulfonated rubber compositions and processes therefor and therewith

Abstract

A sulfonated, oxidized rubber composition and a neutralized, sulfonated, oxidized rubber composition are provided. The sulfonated, oxidized rubber composition, preferably a composition containing such sulfonated, oxidized rubber composition, can be used as an additive in or for asphalt. The neutralized, sulfonated, oxidized rubber composition, preferably a composition comprising such neutralized, sulfonated, oxidized rubber composition, can be used for oil field applications such as preventing the loss of fluids used during such oil field applications. A process of preparing such compositions includes contacting a rubber composition, such as butyl rubber in the form of waste tire particles, with an oxidizing agent to provide an oxidized rubber composition. The oxidized rubber composition is then contacted with a sulfur-containing acid to provide a sulfonated, oxidized rubber composition. The sulfonated, oxidized rubber composition is then contacted with a base to provide a neutralized, sulfonated, oxidized rubber composition.

What is claimed is:  
     
       1. A process of preparing a sulfonated, oxidized rubber composition comprising: 
       contacting a rubber composition with an oxidizing agent under an oxidizing agent-contacting condition to provide an oxidized rubber composition, and  
       contacting said oxidized rubber composition with a sulfur-containing acid under an acid-contacting condition to provide a sulfonated, oxidized rubber composition.  
     
     
       2. A process according to  claim 1  further comprising contacting said sulfonated, oxidized rubber composition with a base under a base-contacting condition to provide a neutralized, sulfonated, oxidized rubber composition. 
     
     
       3. A process according to  claim 2  further comprising drying said neutralized, sulfonated, oxidized rubber composition under a drying condition to provide a dried, neutralized, sulfonated, oxidized rubber composition and further wherein said dried, neutralized, sulfonated, oxidized rubber composition has a particle size in the range of from about 150 micrometers to about 2000 micrometers. 
     
     
       4. A process according to  claim 2  wherein said sulfonated, oxidized rubber composition is subjected to cooling under a cooling condition before said contacting with a base. 
     
     
       5. A process according to  claim 3  wherein said neutralized, sulfonated, oxidized rubber composition is subjected to cooling under a cooling condition before said drying. 
     
     
       6. A process according to  claim 1  wherein said contacting a rubber composition with an oxidizing agent further comprises contacting with a first aqueous medium. 
     
     
       7. A process according to  claim 1  wherein said contacting said oxidized rubber composition with a sulfur-containing acid further comprises contacting with a second aqueous medium. 
     
     
       8. A process according to  claim 1  wherein said rubber is selected from the group consisting of butyl rubber, polychloroprene, sodium rubber, acrylonitrilebutadiene copolymers, butadiene-styrene copolymers, ethylenepropylene-diene rubber, polyisoprene, polyacrylonitrile, silicone, epichlorohydrin, polyurethane, and combinations thereof. 
     
     
       9. A process according to  claim 1  wherein said rubber is butyl rubber. 
     
     
       10. A process according to  claim 1  wherein said oxidizing agent is selected from the group consisting of peroxides, chlorates, perchlorates, nitrates, permanganates, oxygen under pressure, and combinations thereof. 
     
     
       11. A process according to  claim 1  wherein said oxidizing agent is hydrogen peroxide. 
     
     
       12. A process according to  claim 1  wherein the amount of said oxidizing agent is an amount which provides said oxidized rubber composition and further wherein said oxidizing agent-contacting condition comprises a temperature in the range of from about 70° F. to about 120° F., a pressure in the range of from about atmospheric to about 100 pounds per square inch absolute, and a time period in the range of from about 1 minute to about 60 minutes. 
     
     
       13. A process according to  claim 1  wherein said sulfur-containing acid is selected from the group consisting of sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, p-toluene sulfonic acid, methane sulfonic acid, and combinations thereof. 
     
     
       14. A process according to  claim 1  wherein said sulfur-containing acid is sulfuric acid. 
     
     
       15. A process according to  claim 1  wherein the amount of said sulfur-containing acid is an amount which provides said sulfonated, oxidized rubber composition and further wherein said acid-contacting condition comprises a temperature in the range of from about 110° F. to about 300° F., a pressure in the range of from about atmospheric to about 100 pounds per square inch absolute, and a time period in the range of from about 1 minute to about 60 minutes. 
     
     
       16. A process according to  claim 2  wherein said base is selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetramethylammonium bisulfide, tetraethylammonium bisulfide, lithium hydroxide, sodium hydroxide, sodium hydrosulfide, sodium bisulfide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, sodium bicarbonate, sodium carbonate, sodium oxide, sodium sulfide, magnesium oxide, calcium oxide, calcium carbonate, sodium phenoxide, barium phenoxide, calcium phenoxide, and combinations thereof. 
     
     
       17. A process according to  claim 2  wherein said base is sodium hydroxide. 
     
     
       18. A process according to  claim 2  wherein the amount of said base is an amount which provides said neutralized, sulfonated, oxidized rubber composition and further wherein said base-contacting condition comprises a temperature in the range of from about 100° F. to about 200° F., a pressure in the range of from about atmospheric to about 100 pounds per square inch absolute, and a time period in the range of from about 1 minute to about 60 minutes. 
     
     
       19. A process according to  claim 3  wherein said drying condition comprises a temperature in the range of from about 180° F. to about 280° F., a time period in the range of from about 0.1 hour to about 40 hours, and a pressure in the range of from about atmospheric to about 150 pounds per square inch absolute. 
     
     
       20. A composition prepared by the process of  claim 1 . 
     
     
       21. A composition prepared by the process of  claim 2 . 
     
     
       22. A composition prepared by the process of  claim 3 . 
     
     
       23. A composition prepared by the process of  claim 4 . 
     
     
       24. A composition prepared by the process of  claim 5 . 
     
     
       25. A composition prepared by the process of  claim 6 . 
     
     
       26. A composition prepared by the process of  claim 7 . 
     
     
       27. A composition prepared by the process of  claim 8 . 
     
     
       28. A composition prepared by the process of  claim 9 . 
     
     
       29. A composition prepared by the process of  claim 10 . 
     
     
       30. A composition prepared by the process of  claim 11 . 
     
     
       31. A composition prepared by the process of  claim 12 . 
     
     
       32. A composition prepared by the process of  claim 13 . 
     
     
       33. A composition prepared by the process of  claim 14 . 
     
     
       34. A composition prepared by the process of  claim 15 . 
     
     
       35. A composition prepared by the process of  claim 16 . 
     
     
       36. A composition prepared by the process of  claim 17 . 
     
     
       37. A composition prepared by the process of  claim 18 . 
     
     
       38. A composition prepared by the process of  claim 19 . 
     
     
       39. A composition comprising a neutralized, sulfonated, oxidized rubber composition. 
     
     
       40. A composition according to  claim 39  wherein said rubber is selected from the group consisting of butyl rubber, polychloroprene, sodium rubber, acrylonitrilebutadiene copolymers, butadiene-styrene copolymers, ethylenepropylene-diene rubber, polyisoprene, polyacrylonitrile, silicone, epichlorohydrin, polyurethane, and combinations thereof. 
     
     
       41. A composition according to  claim 39  wherein said rubber is butyl rubber. 
     
     
       42. A composition according to  claim 39  wherein said neutralized, sulfonated, oxidized rubber composition has a particle size in the range of from about 150 micrometers to about 2000 micrometers. 
     
     
       43. A composition according to  claim 39  wherein said composition further comprises an aqueous medium. 
     
     
       44. A composition according to  claim 43  wherein said composition further comprises a component selected from the group consisting of clays, polymers, other loss circulation additives, and combinations thereof. 
     
     
       45. A composition according to  claim 44  wherein said clays are selected from the group consisting of montmorillonite, kaolinite, halloysite, vermiculite, attapulgite, smectite, illite, saconite, sepiolite, polygorskite, fuller's earth, chlorite, and combinations thereof. 
     
     
       46. A composition according to  claim 44  wherein said polymers are selected from the group consisting of starches, gums, biopolysaccharides, cellulose, ethers, synthetics, and combinations thereof. 
     
     
       47. A composition according to  claim 44  wherein said other loss circulation additives are selected from the group consisting of paper, cork, saw dust, wood shavings, rock, mica flakes, cloth, cements, silicates, and combinations thereof. 
     
     
       48. A process comprising contacting a composition comprising a neutralized, sulfonated, oxidized rubber composition with a subterranean formation. 
     
     
       49. A process according to  claim 48  wherein said rubber is selected from the group consisting of butyl rubber, polychloroprene, sodium rubber, acrylonitrilebutadiene copolymers, butadiene-styrene copolymers, ethylenepropylene-diene rubber, polyisoprene, polyacrylonitrile, silicone, epichlorohydrin, polyurethane, and combinations thereof. 
     
     
       50. A process according to  claim 48  wherein said neutralized, sulfonated, oxidized rubber composition has a particle size in the range of from about 150 micrometers to about 2000 micrometers. 
     
     
       51. A process according to  claim 48  wherein said composition further comprises an aqueous medium. 
     
     
       52. A process according to  claim 51  wherein said composition further comprises a component selected from the group consisting of clays, polymers, other loss circulation additives, and combinations thereof. 
     
     
       53. A process according to  claim 52  wherein said clays are selected from the group consisting of montmorillonite, kaolinite, halloysite, vermiculite, attapulgite, smectite, illite, saconite, sepiolite, polygorskite, fuller's earth, chlorite, and combinations thereof. 
     
     
       54. A process according to  claim 52  wherein said polymers are selected from the group consisting of starches, gums, biopolysaccharides, cellulose, ethers, synthetics, and combinations thereof. 
     
     
       55. A process according to  claim 52  wherein said other loss circulation additives are selected from the group consisting of paper, cork, saw dust, wood shavings, rock, mica flakes, cloth, cements, silicates, and combinations thereof. 
     
     
       56. A process according to  claim 48  wherein said composition further comprises an aqueous medium and a clay. 
     
     
       57. A process according to  claim 48  wherein said subterranean formation has a temperature in the range of from about 35° F. to about 600° F. and the temperature of said composition is in the range of from about 30° F. to about 150° F. 
     
     
       58. A process comprising: 
       subjecting butyl rubber to particle size reduction to provide a size-reduced butyl rubber having a particle size in the range of from about 150 micrometers to about 2000 micrometers,  
       cryogenically freezing said size-reduced butyl rubber,  
       contacting said size-reduced butyl rubber with an oxidizing agent under an oxidizing agent-contacting condition to provide an oxidized size-reduced butyl rubber,  
       contacting said oxidized size-reduced butyl rubber with a sulfur-containing acid under an acid-contacting condition to provide a sulfonated, oxidized, size-reduced butyl rubber, and  
       contacting said sulfonated, oxidized, size-reduced butyl rubber with a base under a base-contacting condition to provide a neutralized, sulfonated, oxidized size-reduced butyl rubber.  
     
     
       59. A process according to  claim 58  further comprising drying said neutralized, sulfonated, oxidized size-reduced butyl rubber under a drying condition to provide a dried, neutralized, sulfonated, oxidized size-reduced butyl rubber. 
     
     
       60. A process according to  claim 58  wherein said oxidizing agent is selected from the group consisting of peroxides, chlorates, perchlorates, nitrates, permanganates, oxygen under pressure, and combinations thereof; said sulfur-containing acid is selected from the group consisting of sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, p-toluene sulfonic acid, methane sulfonic acid, and combinations thereof; and said base is selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetramethylammonium bisulfide, tetraethylammonium bisulfide, lithium hydroxide, sodium hydroxide, sodium hydrosulfide, sodium bisulfide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, sodium bicarbonate, sodium carbonate, sodium oxide, sodium sulfide, magnesium oxide, calcium oxide, calcium carbonate, sodium phenoxide, barium phenoxide, calcium phenoxide, and combinations thereof. 
     
     
       61. A process according to  claim 58  wherein said oxidizing agent is hydrogen peroxide, said sulfur-containing acid is sulfuric acid, and said base is sodium hydroxide. 
     
     
       62. A process according to  claim 59  further comprising contacting said dried, neutralized, sulfonated, oxidized size-reduced butyl rubber with an aqueous medium and a clay. 
     
     
       63. A process according to  claim 62  further comprising contacting said composition with a subterranean formation. 
     
     
       64. A composition comprising a sulfonated, oxidized rubber composition. 
     
     
       65. A composition according to  claim 64  wherein said rubber is selected from the group consisting of butyl rubber, polychloroprene, sodium rubber, acrylonitrilebutadiene copolymers, butadiene-styrene copolymers, ethylenepropylene-diene rubber, polyisoprene, polyacrylonitrile, silicone, epichlorohydrin, polyurethane, and combinations thereof. 
     
     
       66. A composition according to  claim 65  wherein said rubber is butyl rubber. 
     
     
       67. A composition according to  claim 66  wherein said sulfonated, oxidized rubber composition has a particle size in the range of from about 150 micrometers to about 2000 micrometers. 
     
     
       68. A composition according to  claim 64  wherein said composition further comprises a sulfur-containing acid and a first aqueous medium. 
     
     
       69. A composition according to  claim 68  wherein said sulfur-containing acid is selected from the group consisting of sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, p-toluene sulfonic acid, methane sulfonic acid, and combinations thereof. 
     
     
       70. A process comprising contacting a composition comprising a sulfonated, oxidized rubber composition with asphalt. 
     
     
       71. A process according to  claim 70  wherein said rubber is selected from the group consisting of butyl rubber, polychloroprene, sodium rubber, acrylonitrilebutadiene copolymers, butadiene-styrene copolymers, ethylenepropylene-diene rubber, polyisoprene, polyacrylonitrile, silicone, epichlorohydrin, polyurethane, and combinations thereof. 
     
     
       72. A process according to  claim 71  wherein said rubber is butyl rubber. 
     
     
       73. A process according to  claim 72  wherein said sulfonated, oxidized rubber composition has a particle size in the range of from about 150 micrometers to about 2000 micrometers. 
     
     
       74. A process according to  claim 70  wherein said composition further comprises a sulfur-containing acid and a first aqueous medium. 
     
     
       75. A process according to  claim 74  wherein said sulfur-containing acid is selected from the group consisting of sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, p-toluene sulfonic acid, methane sulfonic acid, and combinations thereof.